Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters

ABSTRACT

Methods and apparatuses are described for contacting an oxidizing solution such as an aqueous hydrogen peroxide composition of hydrogen peroxide and at least one additive that catalyzes the decomposition of the hydrogen peroxide into hydroxyl radicals with an atmospheric effluent containing odorous and/or noxious components. These components are absorbed by the aqueous hydrogen peroxide composition to produce an atmospheric effluent having reduced amounts of the odorous and/or noxious components. Various methods are described for adding the hydrogen peroxide and the decomposition additive.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S.application Ser. No. 10/704,238 filed Nov. 7, 2003, now U.S. Pat. No.7,112,309, which is a divisional of U.S. application Ser. No. 09/797,859filed on Mar. 2, 2001, now U.S. Pat. No. 6,645,450, which claims thebenefit of U.S. Provisional Patent Application No. 60/186,694, filedMar. 3, 2000, all of which are incorporated by reference herein in theirentireties.

BACKGROUND

1. Background of the Invention

This invention relates to the use of hydrogen peroxide reacted withstrong reducing agents or stronger oxidizing agents to produce hydroxylradicals. More specifically, the invention relates to utilizing in-situgeneration of hydroxyl radicals to effectively oxidize odor and/ornoxious compounds found in the food processing industry, such aspoultry, beef, or fish processing, as well as rendering of meat, fish,or fowl by-products. This invention also relates to the use of hydroxylradicals in the reduction of volatile organic compounds in aqueous gasscrubbers.

2. Description of Related Art

In the processing of poultry, beef, and fish, the large volume oforganic material processed, as well as secondary processing (rendering),can generate large quantities of odiferous gases including organicsulfides, thiols, amines, alcohols, inorganic sulfides, ammonia, andsimple carboxylic acids. These compounds are usually the result ofbiological action on the organic materials being processed. The odorsproduced are offensive and can travel significant distances tosurrounding real estate. In other industries, such as chemicalprocessing, paint production, wastewater treatment, etc., noxiouscompounds, such as volatile organic compounds (VOCs), are produced andare subject to environmental air quality regulations.

These gases are usually captured by a water media in air scrubbersystems. In an air scrubber system, typically, air from the processingstep is evacuated into a tower where water, broken into droplets eitherby contact with mixed media or distribution channels, absorbs theodiferous and noxious gas compounds. This water is recirculated anddischarged typically to wastewater treatment systems. U.S. Pat. No.6,015,536 to Lokkesmoe et al., provides a detailed description of theavailable air scrubbing systems on the market and is hereby incorporatedby reference herein.

It can readily be seen that the scrubbing water media will quicklysaturate with the offensive gases and lose its absorbing potential. Atthis point, the water has an intense disagreeable odor. Additives arecommonly injected into the scrubbing water stream to reduce the odorcontent of the aqueous scrubbing media. The water is either dumped tothe wastewater treatment facility or a portion is withdrawn to thewastewater facility and fresh makeup water is added to account for thedifference.

It can also be seen that as the water saturates with gases, particularlynitrogen-bearing gases (ammonia), the pH of the water will riseproportionally. This marked increase in pH reduces the solubility of thegases causing them to flash to the atmosphere. This results in adecrease in the efficiency of the gas transfer to the water media.

Numerous attempts have been made to reduce the odor components in theair scrubbing system. Some technologies attempt to reduce the odor byinjecting a maskant, which is a stronger, more pleasing odor compound.These maskants are extremely expensive, and the duration of theeffectiveness is very short. These compounds do nothing to the actualstructure of the odor molecule.

Maskants are also “fogged” or injected into spray orifices under highpressure to create a small droplet mist effect. These misted materialsare directed into the atmosphere around the odor causing process. Themisted materials either mask the odor or combine with the odor-causingmolecule in the atmosphere to temporarily lower the offensive odor.These compounds, which are usually essential oils, are then blown withthe prevailing winds. These materials are limited by extreme cost and donothing to actually affect the odor-causing molecule.

U.S. Pat. Nos. 4,443,342 and 4,595,577, to Stas et al., describe atreatment method using hydrogen peroxide and copper sulfate as thecatalyst for treatment of wastewater and gases containing organic sulfurcompounds in a pH range below 6.5. It is well known to those of skill inthe art that the efficiency of hydrogen peroxide as an oxidizer isincreased in the pH range of 3 to 6.5. Stas et al. also describe usinghydrogen peroxide in acidic aqueous media with 1 to 5 ppm of ferricsulfate as a catalyst when comparing the efficacy of the use of copper.This catalyst choice, in the amount used, only increases the efficiencyof the hydrogen peroxide and does not effectively reduce the hydrogenperoxide to free radicals in the quantities that would be needed tooxidize odor components to soluble compounds to enable their removal.

Hydrogen peroxide by itself has only moderate success in air scrubbingsystems. It reacts very slowly and is limited in the number of organicmolecules it can oxidize. Some odor reduction can be achieved usinghydrogen peroxide, but it is usually via microbiological control or anincrease in oxygen content of the aqueous scrubbing media.

Halogen donors such as chlorine dioxide, chlorine gas, sodiumhypochlorite, and hypobromous acids have had limited success in the art.The low electronegativity of these halogens (1.0 to 1.7 volts) limitstheir ability to oxidize odor constituents down to simple solublecompounds. Therefore their odor removal efficiency is low compared tothe quantity needed. The use of halogen donors is falling underenvironmental scrutiny due to the formation of haloamines as well astrihalomethanes. Use of these halogens in aqueous streams eventuallycontributes to trihalomethanes and haloamines in surface waters.

U.S. Pat. No. 6,015,536, to Lokkesmoe et al, describes the use ofperoxyacid compounds at a pH of 3 to 6 for odor reduction in airscrubbers. Peroxyacid, namely peracetic acid, is used as an oxidizer ofodor causing molecules, and a reduction of odors from 5 to 50% isdescribed. However, the large doses of peracetic acid needed precludehigher odor removal rates due to cost as well as the contribution of apungent odor from the acetic and peracetic acids. The peracid compoundsalso lack sufficient electronegative potential to break up odor causingcompounds to the degree needed for greater than 50% removal rates.

Ozone has been used with limited success in aqueous gas scrubbers. Ozonehas an inherent high capital expenditure cost and is difficult toutilize the ozone gas in aqueous media. It is difficult to force enoughgas into contact with the aqueous media to effectively oxidize odorcompounds into simple soluble reduced-odor compounds. Ozone is alsocharacterized by large electric utility costs associated with coronadischarge type ozone production units.

Inorganic percompounds, such as percarbonates, persulfates, perborates,and permangenates, have demonstrated odor control potential. Thesecompounds, however, are notoriously slow to liberate oxygen in coldwater at elevated pH.

There exists a need in the art for a treatment process that has a highenough electronegative potential to reduce substantially all odor and/ornoxious compounds to simple, soluble, reduced-odor/noxious, orodor/noxious-free compounds. This treatment process would offer evengreater advance in the art if the process could also eliminate orgreatly reduce the high cost of treating the scrubber water effluent inthe wastewater treatment process.

SUMMARY OF THE INVENTION

In general, the present invention relates to chemical compositions andsystems, including processes and equipment for removing odor and/ornoxious components from an atmospheric effluent. In one embodiment, thechemical composition includes an oxidizer capable of oxidizing the odorand/or noxious components. In another embodiment, the chemicalcomposition includes an aqueous hydrogen peroxide composition ofhydrogen peroxide and an additive that catalyzes the decomposition ofhydrogen peroxide into hydroxyl radicals. When contacted with theatmospheric effluent, the oxidizer or aqueous hydrogen peroxidecomposition oxidizes the odor and/or noxious components to produce anatmospheric effluent having reduced amounts of the odor component and/ornoxious component and, in some embodiments, a non-odor offensive,environmentally acceptable by-product.

A method is described for removing at least one of an odor component anda noxious component from an atmospheric effluent. In one embodiment, theatmospheric effluent is contacted with a solution comprising anoxidizer. In another embodiment, the atmospheric effluent is contactedwith an aqueous hydrogen peroxide composition including hydrogenperoxide and at least one additive that catalyzes the decomposition ofthe hydrogen peroxide to produce hydroxyl free radicals. The odorousand/or noxious component in the atmospheric effluent is absorbed by theoxidizer solution or the aqueous hydrogen peroxide composition andoxidized. In another embodiment, the method further comprises contactingthe gas and liquid in a counter-current fashion. In another embodiment,the oxidizer solution or the aqueous hydrogen peroxide composition canbe collected after contacting the gas in a tank and recycled via arecycle stream to again contact the gas. In this embodiment, additionaloxidizer or additional hydrogen peroxide and decomposition additive maybe added to the recycle stream as required or based upon measurement ofa given solution parameter that is used to indicated whether additionaloxidizer or additional hydrogen peroxide or decomposition additive isrequired. In some embodiments, the measurement of the solution parametermay be done continuously, periodically, or manually. In someembodiments, the addition of the oxidizer or other additives may be doneautomatically using a flow control valve based upon the measured valueof the solution parameter to provide a more precise addition rate ofthese components and better control of the solution composition comparedto a simple on/off valve.

In some embodiments, the decomposition additive comprises a metal-basedcompound, such as a ferrous or ferric salt, such as ferrous sulfate orferric sulfate. In other embodiments, the decomposition additivecomprises ozone, which may be added concurrently with the hydrogenperoxide to the liquid stream to improve contacting between the ozonegas and the hydrogen peroxide in the liquid stream.

In one embodiment, the method for removing an odorous or noxiouscomponent from a gas stream comprises adding hydrogen peroxide, ahydrogen peroxide decomposition additive, and a chelating agent to aliquid stream; contacting a gas stream comprising at least one odorousor noxious component with the liquid stream; and absorbing at least aportion of said odorous or noxious component in the gas stream into theliquid stream. The chelating agent is added to increase the solubilityof the hydrogen peroxide decomposition additive. In some embodiments,the chelating agent allows the pH of the liquid stream to be controlledat a higher value than the liquid stream would otherwise have undersimilar operating conditions without the chelating agent. This mayimprove removal of certain odorous or noxious components. In someembodiments, the decomposition additive comprises a ferrous salt, suchas ferrous sulfate, and the chelating agent comprisesaminopolycarboxylates, such as nitrilotriacetic acid andhydroxyethyliminodiacetic acid; N-heteroxcyclic carboxylates, such aspicolinic acid; polyhydroxy aromatics, such as gallic acid; or othercompounds, such as rhodizonic acid, tetrahydroxy-1,4-quinone, andhexaketocyclohexane.

In some embodiments the pH of chemical composition or the liquid streammay be controlled at a select pH by adding acid or base directly to theliquid stream or to a tank that collects the liquid stream aftercontacting the gas. In other embodiments, the acid or base may be mixedwith the decomposition additive before addition to the chemicalcomposition or the liquid stream or the tank that collects the liquidstream after contacting the gas.

Other advantages of the present invention will become apparent from thefollowing detailed description taken in conjunction with theaccompanying drawings that illustrate, by way of example, the principlesof the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a diagram of one embodiment of a process for removing anodor and/or noxious component from an atmospheric effluent;

FIG. 1A shows a diagram of another control system for the system of FIG.1;

FIG. 1B shows a diagram for a system for adding additive(s) and acid orbase for pH control to one or more gas/liquid contactors or scrubbers;

FIG. 1C shows a diagram for a system for adding an oxidizer to one ormore gas/liquid contactors or scrubbers; and

FIG. 2 shows the system of FIG. 1 within a wastewater effluent system ofa processing plant illustrating the pre-treatment properties of thepresent invention on the waste treatment facility according to oneembodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be more fully described with reference tothe accompanying drawings. To facilitate explanation, the invention willbe described primarily in the context of a particular embodiment,namely, a wet scrubber system comprising a packed column. While theinvention will be described in conjunction with this particularembodiment, it should be understood that the invention can be applied toa wide variety of applications, and it is intended to coveralternatives, modifications, and equivalents as may be included withinthe spirit and scope of the invention as defined by the appended claims.Accordingly, the following description is exemplary in that severalembodiments are described (e.g., by use of the terms “preferably” or“for example”), but this description should not be viewed as limiting oras setting forth the only embodiments of the invention, as the inventionencompasses other embodiments not specifically recited in thisdescription. Further, the use of the term “invention” throughout thisdescription is used broadly and is not intended to mean that anyparticular portion of the description is the only manner in which theinvention may be made or used.

In general, the present invention uses a liquid stream or chemicalcomposition comprising an oxidizer to oxidize absorbed odor and/ornoxious components from an atmospheric gas stream. In some embodiments,additives may also be added to the liquid stream, including, forexample, acid or base to control the pH of the liquid stream, additivesto enhance the effectiveness of the oxidizer (e.g., when using hydrogenperoxide as the oxidizer the additive may be a hydrogen peroxidedecomposition additive that catalyzes the decomposition of hydrogenperoxide to hydroxyl free radicals, chelating agents that, for example,increase the solubility of the hydrogen peroxide decomposition additive,wetting agents, and dispersants). It should be appreciated that anychemical added to the liquid stream may be referred to as an additive.

In one embodiment, the liquid stream comprises an aqueous hydrogenperoxide composition of hydrogen peroxide and at least one additive thatserves to catalyze the rapid decomposition of the hydrogen peroxide intohydroxyl radicals. When contacted with an atmospheric effluentcontaining odor and/or noxious components, the hydroxyl radicals formedoxidize the odor and noxious components to a non-odor offensive,environmentally acceptable by-product. The by-product in combinationwith the aqueous hydrogen peroxide composition form a liquid effluentthat provides charge neutralizing and adsorption species that, inaddition, aid in treatment of wastewater effluents.

As can be seen in Table 1 below, the hydroxyl radical is known in theart as the second most electronegative species, second only to fluorine,and is significantly higher in oxidation potential than other compoundsknown in the art. The highly electronegative hydroxyl radical is,therefore, capable of a much greater decomposition of odor-causingmolecules than any composition known in the art. Accordingly, it is notnecessarily the intent of the invention to utilize the oxidationpotential of the hydrogen peroxide but rather to utilize the hydroxylradical produced from the decomposition of the hydrogen peroxide. Itwill be appreciated that in the decomposition of hydrogen peroxide somediatomic oxygen may also be produced, which also has an oxidationpotential; however, the present invention is directed at utilizing thehydroxyl radical generated from the hydrogen peroxide decomposition.Accordingly, in one embodiment of the invention, at least a portion ofthe hydrogen peroxide in a solution used to contact atmospheric effluentcontaining odor and/or noxious components is decomposed to producehydroxyl radical, which, in turn, oxidizes the odor and/or noxiouscomponents. In another embodiment, although not necessary, it isdesirable to drive the hydrogen peroxide decomposition reaction toproduce predominantly hydroxyl radicals to act in the oxidation of theodor and/or noxious components in the atmospheric effluent. It should beappreciated that neither all of the hydrogen peroxide needs to bedecomposed to hydroxyl radicals nor does the decomposition need toresult in only the production of hydroxyl radicals. In some embodiments,it is sufficient that a portion of the hydrogen peroxide decomposes toproduce at least some quantity of hydroxyl radicals.

TABLE 1 Oxidizer Oxidation Potential (Volts) fluorine 3.0 hydroxylradical 2.8 ozone 2.1 hydrogen peroxide 1.8 potassium permanganate 1.7hypobromous acid 1.6 chlorine dioxide 1.5 chlorine 1.4

FIG. 1 shows a diagram of one embodiment of a process for removing anodor and/or noxious component from an atmospheric effluent. In thisembodiment, a wet scrubber system is used to contact an atmospheric orgaseous effluent comprising an odorous or noxious component with anaqueous hydrogen peroxide composition comprising hydrogen peroxide andat least one additive that catalyzes the decomposition of the hydrogenperoxide to hydroxyl radicals. According to this embodiment, anatmospheric effluent 102 enters a packed scrubber 106 through anatmospheric effluent intake 104. The atmospheric effluent 102 may befrom a food processing process, rendering process, or other industrialprocess that produces an atmospheric or gaseous effluent havingodoriferous and/or noxious components. In this embodiment, the wetscrubber comprises a packed column 108. The atmospheric effluent 102enters the packed column 108 where it is contacted with an aqueoushydrogen peroxide composition 110 supplied by dispenser(s) 112. Theaqueous hydrogen peroxide composition 110 comprises hydrogen peroxideand at least one additive that catalyzes the decomposition of at least aportion of the hydrogen peroxide to hydroxyl radicals. In oneembodiment, the aqueous hydrogen peroxide composition leavingdispenser(s) 112 has a relatively high concentration of hydroxylradicals compared to a hydrogen peroxide solution without such anadditive. In another embodiment, the additive catalyzes thedecomposition to produce predominantly hydroxyl free radicals.

In the packed column 108, the atmospheric effluent 102 and the aqueoushydrogen peroxide composition 110 comprising hydroxyl free radicalscontact each other, and the hydroxyl radicals oxidize the odorous and/ornoxious components in the atmospheric effluent 102 to produce asubstantially non-odor-offensive, environmentally-acceptable by-productthat exits the packed column 108 with the aqueous hydrogen peroxidecomposition 110 as a liquid effluent 114. Dependent on the oxidation ofthe odor and/or noxious component, the liquid effluent 114 may containby-product that is soluble in the aqueous hydrogen peroxide composition110 or that may adsorb onto semi-colloidal particles formed in theaqueous hydrogen peroxide composition 110. The concentration of odorousand/or noxious components is reduced in the atmospheric effluent 102,which exits the packed column 108 as a gaseous exhaust effluent 116 byway of a vent 118.

The liquid effluent 114 exits the packed column 108 and is collected ina reservoir 120 for discharge to a wastewater facility. In someembodiments, the reservoir is integral to the scrubber or packed column108, in which case, the reservoir 120 may also be vented. In someembodiments, the liquid effluent 114 may be collected and the entirereservoir 120 dumped into a waste treatment pathway or waste treatmentfacility. In other embodiments, the reservoir 120 may be equipped withan overflow system so that a portion of the liquid effluent 114 iscontinually or periodically overflowed into a waste treatment pathwayfor delivery to a waste treatment facility. In the latter case, thereservoir 120 may also have an add-back line to allow introduction ofmakeup water into the reservoir 120 so that a constant effluent level ismaintained in the reservoir 120.

A recycle line or sidestream 121 in fluid communication with thereservoir 120 and the dispenser(s) 112 is used to transfer liquideffluent 114 from the reservoir back to the top of the packed column 108by using a pump 122 within the recycle line 121. The fluid in thisrecycle line or sidestream 121 may be referred to as a recycle stream orfluid. Those of skill in the art will appreciate that a wide variety ofpumps may be used. The pump should be chosen to provide sufficient powerto move fluid at the mass flow rate required by the particular scrubber.It should also resist chemical attach by the liquid effluent and anyadditives present in the liquid effluent. For certain applications, itmay be desirable to use specific types of pumps. For example, asdescribed below, when using the pump to introduce ozone or other gaseouscatalysts, a pump capable of introducing a gas into a liquid streamcould be used, such as a regenerative turbine pump.

It will be appreciated that at the start of the process the contents ofthe reservoir 120 may be essentially makeup water until the process hascompleted several cycles in which the aqueous hydrogen peroxidecomposition 110 has been contacted with the atmospheric effluent 102.Aqueous hydrogen peroxide and any additives are added to the liquideffluent 114 in the recycle line or sidestream 121 to form the aqueoushydrogen peroxide composition 110, which is then delivered to theatmospheric effluent 102 in the packed column 108 via dispenser(s) 112.

The hydrogen peroxide in the aqueous hydrogen peroxide composition isdelivered from a source container 124 into the recycle line orsidestream 121 via an inlet valve 126, which is positioned upstream ofthe pump 122. The concentration of hydrogen peroxide in the sourcecontainer 124 should be chosen to allow safe handling given theequipment in use and to provide sufficient concentration for the needsof the scrubber. Although the concentration of hydrogen peroxide in thesource container 124 may be selected within a wide range, specificembodiments will range between about 35% to 50% by weight in an aqueoussolution as these ranges are currently industrially available andlegally transportable. In a preferred embodiment, the concentration isabout 50% by weight in aqueous solution.

At least one decomposition additive in the aqueous hydrogen peroxidecomposition is delivered from a source container 128 into the recycleline or sidestream 121 via an inlet valve 130, which is positioneddownstream of the pump 122. Upon the addition of the additive on thedownstream side of the pump 122, the decomposition of at least a portionof the hydrogen peroxide to hydroxyl radicals is catalyzed. In anotherembodiment, the decomposition produces predominantly hydroxyl radicals.As noted above, it is not necessary that all of the hydrogen peroxidedecompose to hydroxyl radicals or that the decomposition itself onlyproduce hydroxyl radicals. Depending upon the amount of hydroxylradicals produced, which can be determined based upon the removalefficiency of the odorous and/or noxious components from the gas stream,the rate and amount of additive delivered to the system can be adjusted.Addition of the additive on the backstream or downstream side of thepump 122 is preferred over arrangements on the vacuum side as it reduceswear on the pump 122 from the decomposition product of hydrogenperoxide, e.g., the hydroxyl radicals. However, it should be appreciatedthat the additive may be added upstream of the pump 122 using a similarinlet valve. The aqueous hydrogen peroxide composition comprising thehydroxyl radicals is then delivered to the packing column 108 viadispensers 112 to contact the atmospheric effluent 102.

In some embodiments, the aqueous hydrogen peroxide composition mayinclude additional additives, including additives that catalyze thedecomposition of hydrogen peroxide, wetting agents, and/or chelatingagents (discussed further below). Addition of these additives would bemade similar to the addition of the additive for catalyzing thedecomposition of the hydrogen peroxide discussed above. Thus, there maybe separate source containers and inlet valves to enable the regulateddelivery of these additional additives in aqueous form to the recycle orsidestream 121. Preferably, these additional additives are added on thedownstream side of the pump 122; however, these additives could be addedat other locations, including, for example, anywhere along the recycleline or sidestream 121 or directly to the reservoir 120. Additionally,some or all of the other additives, wetting agents, and/or chelatingagents may be mixed together and delivered from a single sourcecontainer. Alternatively, any one or more of these additives may beprovided together with one or more other source materials. For example,the hydrogen peroxide in its source container 124 may contain any one ormore chemically compatible (e.g., resistant to oxidation) additives suchas certain chelating agents and/or wetting agents. Of course, theadditives may also be provided with the decomposition additive from itssource container 128 and/or from the source container 140 for the acidor base (discussed further below).

It will be appreciated that the inlet valves discussed in FIG. 1 areregulated so that the aqueous hydrogen peroxide composition in therecycle line or sidestream 121 has a desired composition. Regulation ofthe inlet valves may be by any means, such as a controller or formulatorsystem, such that the individual components are delivered into therecycle or sidestream 121 in the desired amounts to form the aqueoushydrogen peroxide composition. Further, this system for feeding thesecomponents may stand-alone or be incorporated as part of a largercontrol system, particularly in the case where the system includes morethan one scrubber. It will be appreciated that other embodiments may beutilized in which the components of the aqueous hydrogen peroxidecomposition are added at different locations within the system,including different locations along the recycle or sidestream 121 ordirectly to the reservoir 120.

One of skill in the art will appreciate that the actual composition ofthe aqueous hydrogen peroxide composition in the recycle line orsidestream 121 and, specifically, the concentration of hydrogenperoxide, the additive, and hydroxyl free radicals therein, isdetermined based upon the composition of the gas stream entering thescrubber and the specific gaseous components to be removed, as well asthe scrubber operating conditions. At a given set of scrubber operatingconditions (such as the gas flow rate and concentration of odorousand/or noxious components and the liquid flow rate through thescrubber), the addition rate of either or both of the hydrogen peroxideand the additive may be adjusted to provide the necessary production ofhydroxyl free radicals to achieve the desired removal rate of odorousand/or noxious components. Of course, the concentration of the hydrogenperoxide and the additive in their respective source containers may beadjusted to achieve the desired rate of addition of each to the systemin balance with overall water balance considerations.

The system and process of the embodiment of FIG. 1 may also include a pHcontrol loop to measure the pH of the liquid effluent 114/aqueoushydrogen peroxide composition 110 in the recycle line or sidestream 121and, in response, to regulate the addition of an acid or base into therecycle line or sidestream 121 to maintain the pH of that stream withina preferred pH range. In such an embodiment, an inlet valve 132 permitsthe withdrawal of a portion of the aqueous stream in the recycle line orsidestream 121. This stream contacts a pH probe 134 and passes back tothe packed scrubber 106 or the reservoir 120. The pH probe 134 measuresthe pH of this stream and communicates the measured pH to a pHcontroller 138. The pH controller 138 then regulates, as needed, theaddition of an acid or base from an acid or base source container 140into the recycle line or sidestream 121 via an inlet valve 142. In oneembodiment, the inlet valve 142 is located upstream of the inlet valve126. In another embodiment, the acid or base is added to the streamwithdrawn from the recycle line or sidestream 121 that contacts the pHprobe (not shown). In this case, the acid or base would be addeddownstream of the pH probe before this stream is returned to thereservoir 120. In another embodiment, the acid or base can be addeddirectly to the reservoir 120 (not shown).

Through the addition of acid or base using the pH control loop, the pHof the liquid effluent 114/aqueous hydrogen peroxide composition 110 inthe recycle line or sidestream 121 is maintained at a level thatmaximizes the decomposition of the hydrogen peroxide by the additive(s)that catalyze such decomposition. This, in turn, allows the removal ofthe odor and/or noxious component from an atmospheric effluent to beoptimized. One of skill in the art will appreciate that the optimal pHto be used will be dependent upon the particular gaseous component to beremoved and oxidized and its properties and concentration in theatmospheric effluent, as well as the composition of the aqueous hydrogenperoxide composition and operating conditions of the scrubber. Forexample, in removing hydrogen sulfide, its solubility is pH dependentand increases with increasing pH above about pH 5 to about pH 9.5.Accordingly, this solubility property needs to be taken into account inselecting an operating pH. Additionally, the solubility of thedecomposition additive, particularly a metal-based additive (discussedbelow), relative to the pH of the aqueous hydrogen peroxide compositionneeds to be taken into account. Typically, metal-based additives areless soluble at higher pH, so that the pH may need to be controlled at alower level to maintain an adequate concentration of such an additive insolution and available to catalyze the decomposition of the hydrogenperoxide.

As described above, at least one additive is added to form, inconjunction with the added hydrogen peroxide, the aqueous hydrogenperoxide composition. This additive is used to catalyze thedecomposition of hydrogen peroxide to hydroxyl free radicals. Generally,the catalyst source is chosen relative to the gas stream being treatedand the specific gaseous components to be removed so as to generate anaqueous hydrogen peroxide composition having optimal concentrations ofhydroxyl free radicals. The catalyst source is also selected with a viewtoward safety and effectiveness. Obviously, the concentration of thecatalyst used will vary depending upon the particular catalyst chosenfor the task. Typically, the catalyst will be delivered using an aqueoussolution, although for some catalyses, such as ozone and certain of thegroup VII elements (discussed further below), a direct gaseous additionwill be necessary.

In one embodiment, the additive used is ferrous sulfate. The use offerrous sulfate in sufficient quantities to catalyze the decompositionof the hydrogen peroxide into hydroxyl radicals is well known to thoseof skill in the art as “Fenton's Reagent”. However, the use of thehighly electronegative hydroxyl radicals has not been explored in airscrubbers, such as those utilized in food processing and in otherprocess industries that produce atmospheric effluents, such asrendering, containing odor and/or noxious components, for example,volatile organic compounds (VOCs).

In aqueous media, ferrous iron decomposes hydrogen peroxide in thefollowing manner:

As earlier described, the hydroxyl radical formed oxidizes the odorproducing components and/or noxious components via electron transfer.

It should be appreciated that the solubility limit of the catalystpresents an upper bound on concentration of the catalyst in the sourcecontainer. In the case of ferrous sulfate, the concentration may beselected within a wide range with specific embodiments within the rangebetween about 20% to about 38% by weight in aqueous solution. In apreferred embodiment the concentration of ferrous sulfate is about 38%by weight in aqueous solution. In this embodiment, the aqueous hydrogenperoxide composition may be added as a 50% by weight hydrogen peroxidesolution in its source container.

The ratio by weight of the hydrogen peroxide solution to the ferroussulfate, based on a 50% by weight hydrogen peroxide solution and a 38%by weight ferrous sulfate solution should be within the range betweenabout 1:1 to about 100:1, with a preferred ratio within the rangebetween about 2:1 to about 50:1, and with a most preferred ratio withinthe range between about 5:1 to about 15:1. The higher the ferroussulfate ratio the more the decomposition reaction is driven to producinghydroxyl free radicals. The ratio can be as high as one part 50% byweight hydrogen peroxide solution to ten parts 38% ferrous sulfatesolution, but an extreme amount of heat is generated. While this amountof heat may be acceptable in some settings, it may not be desirable inothers.

It should be appreciated that the use of highly electronegative hydroxylradicals is capable of a much greater decomposition of odor-causingmolecules than any composition known in the art. Further, the use ofsome of the decomposition additives, particularly, ferrous sulfate, notonly reduces the hydrogen peroxide into the hydroxyl radicals but alsointroduces a semi-colloidal substrate into the aqueous media that iscapable of effectively adsorbing odor-causing and/or noxious compounds.

As noted above, in some embodiments, additional additives may be addedto the aqueous hydrogen peroxide composition, their choice depending onthe particular system in which they will be used, cost, environmentalconcerns, and organic loading of the effluent being treated. Theseadditional additives may include additional catalysts or other additivesand may be added alone or in combination, such as wetting agents,dispersant polymers, and chelating agents.

Additives that act as catalysts, other than ferrous sulfate, may be usedalone or in combination with ferrous sulfate. In one embodiment, thecatalytic additive may be any element chosen from elements in groups 3B,4B, 5B, 6B, 7B, 8B, 1B, and 2B of the Periodic Table of Elements and mayinclude combinations thereof. It will be readily apparent to one ofnormal skill in the art that the additive(s) selected from theseelements would be chosen based upon cost, speed of reaction andenvironmental impact. Among these elements, iron and its conjugates arethe cheapest, most readily available, and are of lowest environmentalimpact.

More preferred are the “d” block transition elements, characterized bythe “d” electrons in their valence shell, and combinations thereof. Forexample, the additive may be cobalt. In one embodiment, the aqueoushydrogen peroxide composition may be formed using an amount of cobaltwithin the range between about 0.5% wt/wt % to about 1% wt/wt % of thetotal aqueous hydrogen peroxide composition. Or, the amount of cobaltmay be between about 0.5% wt/wt % to about 1% wt/wt % of a solutioncomprised of cobalt and a 50% by weight hydrogen peroxide solution. Inanother embodiment, the additive may be any element selected fromelements in Group 7A of the Periodic Table of Elements and combinationsthereof, for example, fluorine.

In one embodiment, the decomposition additive may be ozone. Using ozoneas the additive to catalyze the decomposition of the hydrogen peroxideprovides numerous advantages. In particular, using ozone allows foroperation at higher pH because the ozone is not as solubility limited athigher pH compared to the decomposition additives that comprise metals.As discussed below, the solubility of a metal-based decompositionadditive typically decreases at higher pH, but a chelating agent may beused to enhance its solubility. The use of ozone, however, may displacethe need to use a chelating agent in combination with a metal-baseddecomposition, thereby allowing operation at higher pHs. As noted above,operation at higher pH provides the aqueous hydrogen peroxidecomposition with a greater capacity to absorb acidic odorous and noxiouscomponents in the gas stream to be treated, thereby increasing theremoval efficiency of the process. Accordingly, when using ozone,because solubility of a metal-based catalytic additive is not an issue,the pH of the aqueous hydrogen peroxide composition may be increased.The particular pH used in operation can be determined as discussed aboveand is based upon factors such as the type and concentration of theodorous and/or noxious components in the gas stream and the operatingconditions of the scrubber. Generally, it should be appreciated thatvirtually any pH above, for example, 5.0, may be used.

When using ozone very poor gas transfer to liquid media has beenobserved in the art. As part of the present invention, use of aregenerative turbine pump, for example, a Burks regenerative turbinepump manufactured by Burks Manufacturing, can be used as the pump forthe recycle line or sidestream to provide sufficient to excellent mixingof the ozone with the liquid stream in the recycle line or sidestream.Referring back to FIG. 1, such a regenerative turbine pump can be usedas the pump 122 in the recycle or sidestream 121. In this case, thehydrogen peroxide is added as shown in FIG. 1 upstream of or on thevacuum side of the regenerative turbine pump 121. An ozone/air mixtureis then added to an inlet port pre-built on the vacuum side of theregenerative turbine pump 121. The resulting liquid discharged from theregenerative turbine pump 121 provides a well mixed stream. Inparticular, pressurizing the discharge side of the pump to a minimum of100 psi by using a pinch valve (not shown) gives excellent gas transferof the ozone to the liquid media in the recycle line or sidestream. Inthis instance, rather than the ozone being delivered through the inletvalve 130 used for other liquid phase additives, the ozone would insteadbe connected to the inlet port pre-built on the vacuum side of theregenerative turbine pump 122 and regulated through the pinch valve. Itwill be appreciated that this pinch valve may also be controlled usingthe same control system or formulator system that regulates the otherinlet valves of FIG. 1. It should be appreciated that in someembodiments, the ozone may be added either upstream or downstream of thecirculation pump or in any other manner to maximize the transfer of theozone into the liquid phase and the decomposition of the hydrogenperoxide.

More particularly, as the liquid effluent 114, enriched with hydrogenperoxide (due to the addition of hydrogen peroxide from the hydrogenperoxide source container 124), enters the vacuum side of theregenerative turbine pump 122, the air/ozone mixture is introducedthrough a pre-machined air port. Intense shear is developed inside theregenerative turbine pump 122 that breaks the ozone/air mixture intomicrobubbles entrained in the liquid solution. The discharge from theregenerative turbine pump 122 is pressurized to a minimum of 100 psithrough a pinch valve assembly, ensuring solubilization of the ozoneinto the liquid effluent 114 enriched with hydrogen peroxide. Thisallows for the efficient decomposition of the hydrogen peroxide by theozone into hydroxyl radicals.

In another embodiment, a nonionic wetting agent may be added to thescrubber or to the aqueous hydrogen peroxide composition to enhance itsactivity by allowing further penetration of the oxidizing agent intocrevices of bacterial forms of odor and/or noxious components. While theexact mechanism is not known, it is believed that certain nonionicsurfactants, i.e., wetting agents, assist in the degradation ofbacterial cell walls allowing the aqueous hydrogen peroxide compositionto more readily kill the bacteria in the medium.

Preferred wetting agents are octylphenols, ethylene oxide blockcopolymers, propylene oxide block copolymers, and combinations thereof.The determining factors for wetting agent choice is organic loading ofthe effluent, i.e., the level of proteins or starches in the effluent,cleanliness of the system being treated, i.e., the amount of depositsand slime on the surfaces of the scrubber tank and packing, as well asneed for defoaming capabilities.

In one embodiment, the wetting agent, as 100% active material, ispresent in an amount up to about 10% by weight of the aqueous hydrogenperoxide composition (in the scrubber or as additives to a scrubbersidestream), with a preferred embodiment being an amount up to about 5%by weight of the aqueous hydrogen peroxide composition, and in a mostpreferred embodiment an amount up to about 1% by weight of the aqueoushydrogen peroxide composition.

In another embodiment, a low molecular weight dispersant polymer may beadded to the scrubber or to the aqueous hydrogen peroxide composition inorder to prevent iron and other particle agglomeration in the aqueousmedia as well as to prevent iron and organic deposition in lower liquidflow areas. In one embodiment, the average molecular weight of these lowmolecular weight dispersants is within the range between about 1,000 toabout 22,000, with a preferred average molecular weight within the rangebetween about 1,000 to about 9,000. These low molecular weightdispersants may be, but are not limited to, homopolymers of acrylicacid, methacrylic acid, acrylamide, copolymers and terpolymersacrylates, methacrylates, acrylamide, AMPS (2-acrylamido-2-methylpropane sulfonic acid), and combinations thereof. For example, adispersant resistant to oxidation may be desirable in situations wheresulfur-based compounds that are formed as a result of operation athigher pHs and interaction with a metal-based decomposition additive inwhich insoluble agglomerations, such as zinc sulfate, are formed.

The low molecular weight dispersant polymer is added on a weight percentbasis (i.e., wt/wt % on the total composition weight of the aqueoushydrogen peroxide composition in the scrubber or as additives to ascrubber sidestream). A preferred percentage of the low molecular weightdispersant, in the aqueous hydrogen peroxide composition, is within therange between about 0.5% active wt/wt % to about 10% active wt/wt % ofthe total aqueous hydrogen peroxide composition. A more preferredpercentage is within the range between about 0.5% active wt/wt % toabout 5% active wt/wt % of the total aqueous hydrogen peroxidecomposition, and a most preferred percentage is within the range betweenabout 0.5% active wt/wt % to about 2% active wt/wt % of the totalaqueous hydrogen peroxide composition.

In another embodiment, a chelating agent may be added to the aqueoushydrogen peroxide composition. As earlier discussed, a semi-collodialmetal complex may form during the oxidation process, and in someinstances, the development of this colloidal metal complex isundesirable. A chelating agent may be added to prevent the formation ofmetal hydroxides or other insoluble metal complexes. In one embodiment,the chelating agents may be organic acids such as gluconic acids,glycolic acids, lactic acids, and combinations thereof. It will beappreciated that a large number of chelating agents may also be used andtheir selection readily apparent to those of skill in the art; however,the chelating agent should not be of such potent chelating ability as toprevent the availability of the metal complex for decompositionpurposes.

A chelating agent may also be added to enhance the solubility of thedecomposition additive or catalysts. This may, in some embodiments,allows for operation at higher pH. As noted above, higher pH increasesremoval of the odorous and/or noxious components in the gas compared tolower pH operation. It should be appreciated, however, that a chelatingagent may be used to enhance the solubility of the decompositionadditive in some embodiments where increasing the pH may not benecessary.

Generally, chelating agents can be selected based upon the particulardecomposition additive being used. For example, chelating agents knownin the art may be used to increase the solubility of metal-baseddecomposition additives, such as ferrous ion and other metal complexes.In addition, ferric (Fe³⁺) ion may be used as the decomposition additiveto decompose hydrogen peroxide to produce hydroxyl radicals, andchelating agents may be added to increase the solubility of the ferricion, thereby increasing the production of hydroxyl free radicals andallowing for operation at a higher pH. Chemical Treatment of PesticideWastes—Evaluation of Fe(III) Chelates for Catalytic Hydrogen PeroxideOxidation of 2,4-D at Circumneutral pH, Sun et al., J. Agric. Food Chem,1992, 40, 322-327, which is incorporated by reference herein, describesseveral chelating agents that may be used to solubilize ferric ion. Suchchelating agents that showed “high” catalytic activity and that may beused in the present invention include: aminopolycarboxylates, such asnitrilotriacetic acid and hydroxyethyliminodiacetic acid;N-heteroxcyclic carboxylates, such as picolinic acid; polyhydroxyaromatics, such as gallic acid; and other compounds, such as rhodizonicacid, tetrahydroxy-1,4-quinone, and hexaketocyclohexane. These chelatingagents may be used separately. However, it may be possible to usemixtures of these chelating agents as well.

It should be appreciated that the chelating agent and the decompositionadditive, such as ferrous ion or ferric ion (which may be added, forexample, as ferric sulfate) may be mixed before use to allow forchelation. For example, referring to FIG. 1, the chelating agent and theferric ion may be chelated prior to placing such a mixture in theadditive source container 128. In this case, the selection of thedecomposition additive and chelating agent can be based upon thespecific application or particular gaseous components to be removed andthe desired operating pH. By mixing the decomposition additive and thechelating agent prior to use, this mixture is essentially “tailor-made”and is ready for immediate use in the particular application at issue.In fact, this mixture can be prepared remote from the facility where itwill be used and shipped to that facility for immediate use.

Alternatively, the decomposition additive and the chelating agent may beadded separately to the additive source container 128, thereby allowingfor in-situ chelation in the source container 128. In this case,consideration must be given to the rate at which this solution is addedthrough the valve 130 to the system to provide sufficient time forchelation to occur. One of skill in the art will appreciate theconditions necessary to chelate, including use of the proper pH, whichmay be, for example, pH 6. Alternatively still, the chelating agent maybe added through the use of a separate source container (not shown) in amanner similar to that of the additive source container 128. Further,the use of a separate source container for the chelating agent may beused to dispense the chelating agent into the recycle line or sidestreameither upstream or downstream of the pump 122; however, it is preferableto dispense the chelating agent into the recycle line or sidestream asclosely as possible to the point where the additive is added to therecycle line or sidestream.

As noted above, use of a chelating agent to increase the solubility ofthe decomposition additive (for example metal-based additives and, inparticular, ferrous or ferric ions) allows for operation at a higher pHin the aqueous hydrogen peroxide composition that is fed to thescrubber. Operation at higher pH increases the capacity of the aqueoushydrogen peroxide composition to absorb additional acidic gases, therebyincreasing the removal efficiency of the process. It should beappreciated that the specific pH used will be dependent upon theparticular gaseous components to be removed from the gas stream and,correspondingly, may include a wide range of pHs. In some embodiments,it may be desirable to not change the operating pH significantly or atall upon the addition of a chelating agent.

The present invention has been described above primarily with referenceto removal of odor and/or noxious components from an atmosphericeffluent in which the oxidized odor and/or noxious components areoxidized during contact with an aqueous hydrogen peroxide composition toproduce a substantially non-odor offensive, environmentally acceptableby-product that is solubilized in or adsorbed into the aqueous hydrogenperoxide composition to form a liquid effluent. It should beappreciated, however, that various oxidizers or solutions containingoxidizers may be used. For example, oxidizing compounds such as chlorinegas, sodium hypochlorite, hypobromous acid, chlorine dioxide, hydrogenperoxide, peroxy acids, ozone, and permanganate may be used.

In addition, the present invention has been described above in thecontext of one embodiment: the use of a wet scrubber system using asingle packed column with a single integrated reservoir. It should beappreciated that other gas/liquid contactors may be used in the wetscrubber system. For example, spray towers, Venture spray condensers, ora combination of spray towers and packed columns may be used. Further,counter-current scrubbers, where the direction of the gas flow isopposite the direction of the liquid flow; co-current scrubbers, wherethe direction of the gas flow is in the same direction as the liquidflow; and cross-flow scrubbers, where the direction of the gas flow isat an angle to the direction of the liquid flow; may be used. Inaddition, it should be appreciated that more than one reservoir may beused for a single scrubber or, alternatively, one reservoir may be usedfor more than one scrubber. Further, it should be appreciated that thereservoir does not necessarily need to be integral to the gas/liquidcontactor and may be a separate tank, provided that appropriate gasseals are in place.

It should be appreciated that more than one gas/liquid contactor may beused in a single system. Such gas/liquid contactors may be of the sameor various types and may be configured to operate in series or inparallel. Each gas/liquid contactor could also have its own reservoir ormultiple gas/liquid contactors may share the same reservoir. In usingmore than one gas/liquid contactor with one or more reservoirs, it ispossible to utilize one set of source containers for hydrogen peroxide,additives, and any acid or base required for pH control.

FIG. 1A illustrates another control system for the system of FIG. 1. Asnoted above, the addition of the hydrogen peroxide and the decompositionadditive, as well as other additives, is regulated to provide thedesired composition in the liquid solution in the scrubber. Similar tothe pH control loop discussed above, FIG. 1A shows a probe 135 that isdesigned to measure a given solution parameter or measurable parameterthat can be used to control the addition rate of the hydrogen peroxideor the additives or both. For example, the probe 135 may measure theoxidation-reduction potential of the solution or a particular chemicalspecies, such as a given additive, a species that is indicative of theconcentration of the additive, the concentration of gaseous speciesabsorbed by the scrubber, or a combination of these. This probe 135 maybe placed in a sidestream similar to the one described above inconnection with the pH probe 134. A controller 139 may be used toreceive the output from the probe 135 and in response automaticallycontrol the addition rate via the pumps that add the hydrogen peroxidefrom its source container 124 or the additive from its source container128. In one embodiment, the hydrogen peroxide addition rate may be setat a given, constant value, and the probe 135 and controller 139 wouldbe used to control the addition rate of the decomposition additive (asshown by the solid line between the controller 139 and the sourcecontainer 128 for the additive). Alternatively, the rate of addition ofthe decomposition additive may be set at a given, constant value, andthe probe 135 and controller 139 would be used to control the additionrate of the hydrogen peroxide (as shown by the dashed line between thecontroller 139 and the source container 124 for the hydrogen peroxide).It should be appreciated, that separate control loops may be used forthe hydrogen peroxide and the additive, respectively, depending upon thetype of probe used and the solution parameter that is being measured. Itshould also be appreciated that a pH control loop may be used incombination with the control loop shown in FIG. 1A.

FIG. 1B shows a diagram for a system for adding additive(s), such as thedecomposition additive and other additives described above, and acid orbase for pH control to one or more gas/liquid contactors or scrubbers.As noted above, a system may include more than one scrubber/reservoircombination. In the system shown in FIG. 1B, each source container foreach additive and for acid or base (e.g., a ferrous sulfate sourcecontainer 150 and a source container for acid or base for pH control152) is fluidly connected to a single feed tank 154. The feed tank 154may have a level controller 155 that is used to control the additionrate of the additive(s), the acid or base, the make-up water, or acombination of these to the feed tank 154. Of course, the concentrationof the additive(s) and acid or base in their respective sourcecontainers 150, 152 will need to be accounted for in determining theiraddition rate to the feed tank 154 or visa versa. It should beappreciated that while FIG. 1B is shown for use in adding additives andacid or base to multiple scrubbers, the use of a single tank 154 formixing additives and acid or base may be used for systems having onlyone scrubber/reservoir as well.

The feed tank 154, accordingly, comprises a solution 156 of the variousadditives fed to it and any desired acid or base for pH control of therecirculating solution for each scrubber. Depending upon the additive orcombination of additives used, the chemical effect of the addition ofacid or base to the feed tank 154 on any such additives needs to beconsidered to ensure that the desired chemical effect of the additiveswould not be adversely altered before its addition to the scrubbers.

The feed tank 154 is fluidly connected to a distribution pump 158 thatis fluidly connected to each scrubber's recycle line or sidestream (notshown) via a flow control valve 159 at the desired location along eachrecycle line or sidestream. One desired location for distributing thesolution 156 from the feed tank 154 to each recycle line or sidestreammay be downstream of each scrubber's recycle line or sidestream pump, asshown, for example, by the relative location of the additive additionvia the valve 130 to the pump 122 in FIG. 1. It should be appreciated,however, that the point of addition to each scrubber may vary fromscrubber to scrubber and may include points other than the recycle lineor other or additional points along the recycle line. In other words,the solution 156 may be added to different locations along eachscrubber's recycle line or at different points for each scrubber, suchas each scrubber's reservoir.

The flow control valve 159 may be any flow control valve, including avalve having precise control over the flow rate that passes through it,such as an analog valve, or, alternatively, an on/off valve. In eithercase, the flow control valve 159 may be controlled based upon a certainsolution parameter measured, either on a continuous, semi-continuous orperiodic, or manual basis, in each scrubber's recycle line or in eachscrubber's reservoir. The solution parameter measured may be theconcentration of any chemical species or solution specific measurementthat provides information that can be used to determine whether to addadditional additive(s). The solution parameter may include suchparameters as pH, oxidation reduction potential, the concentration ofthe decomposition additive or a particular chemical species indicativeof the concentration of the additive, the concentration of gaseousspecies absorbed by the scrubber, or a combination of these as furtherdescribed below. In some embodiments, the measurement of the solutionparameter is done automatically either on a continuous, semi-continuousor periodic basis, and the results of such measurement are used toautomatically control the flow control valve 159. Of course, therequired feed rate of the solution 156 in the feed tank 154 to eachscrubber will be based upon each particular application, including, forexample, the particular noxious components to be removed, the amount ofgas being treated, and the operating conditions of each scrubber (e.g.,the recirculation rate of the aqueous hydrogen peroxide compositionthrough the scrubber) and the concentration of the various components inthe solution 156 in the feed tank 154.

In operation, the addition rate of the solution 156 from the feed tank154 to each recycle line or sidestream of each scrubber may becontrolled in various manners. In some embodiments, the addition of thissolution 156 is controlled by the pH control loop on each recycle lineas described above in connection with FIG. 1. In this case, a separatepH controller would be used for each scrubber and would control arespective flow control valve 159 to determine the flow rate of solution156 from the feed tank 154 to that scrubber's recycle line. In otherembodiments, different solution parameters could be monitored and usedto control the addition rate of the solution 156 from the feed tank 154by the flow control valve 159. As noted above, oxidation reductionpotential, the concentration of the decomposition additive or aparticular chemical species indicative of the concentration of theadditive, the concentration of gaseous species absorbed by the scrubber,or a combination of these could be monitored and used to control theaddition rate of the solution 156.

As described above, depending upon the specific application, theconcentrations of the additive(s) and the acid or base in the solution156 can be adjusted so that the appropriate amount of each is fed toeach scrubber. In addition, the relative concentrations in the solution154 in the feed tank 156 may need to be adjusted for each specificapplication so that the appropriate amount of each additive and acid orbase can be fed to each scrubber. This can be accomplished by adjustedthe concentration of the additives and the acid or base in theirrespective source containers 150, 152. Further, these concentrationsmust be adjusted to be consistent with each scrubber's and the overallsystem water balance.

It should be appreciated that using a flow control valve 159 allows formore precise control of the flow rate to each scrubber, as opposed to asimple on/off valve, in combination with monitoring either pH or anothersolution parameter provides for better control of the solution chemistryand removal of the noxious and odorous components. Particularly bymonitoring the pH or another solution parameter in the recycle stream,as shown in FIGS. 1 and 1A, the composition of the solution that iscontacting the gas stream is more well known than, for example,monitoring the solution in the reservoir. Further, by adding theadditive and/or acid or base directly to the recycle stream based uponthe results of monitoring of the solution in the recycle stream allowsthe recycle stream chemistry to be properly controlled or adjusted justprior to entering the scrubber. This allows for more optimal control ofthe removal of the noxious and odorous components.

Optionally, any make-up water required for each reservoir may also beadded to the feed tank 154. In this case, the dilution effect of anywater added to the feed tank 154 must be taken into account so that thedesired amount of each additives and acid or base are ultimately addedto each recycle line. In addition, the water make-up needs of eachreservoir, to the extent that they are different, must be taken intoaccount. In other words, a water balance must be achieved for theoverall system, which will also impact the amount of water in the feedtank 154, as discussed above. Alternatively, make-up water may be addeddirectly to each scrubber's reservoir.

In the system as shown in FIG. 1B and as described above, the hydrogenperoxide can be added from separate source containers directly to therecycle line or sidestream of each scrubber, or a single sourcecontainer can be used with a distribution system to each recycle line orsidestream of each scrubber. Preferably, the hydrogen peroxide would beadded upstream of each scrubber's recycle or sidestream pump, such asshown by the relative location of the additive addition via the valve126 to the pump 122 in FIG. 1. In all cases, a control valve would beused to monitor and regulate the flow of hydrogen peroxide for eachscrubber. The control of such a control valve could be based upon theremoval efficiency of each scrubber or it could be based upon therelative addition rate of the decomposition additive to the recycle lineof each scrubber.

As an alternative to FIG. 1B, each source container of additive or acidor base may be separately connected to a separate corresponding mainheader line that is fluidly connected to each recycle line or sidestreamof each scrubber at the desired location along the recycle line orsidestream (not shown). In other words, the source container for eachadditive would be separately connected to each scrubber via its own mainheader line. As described above, one desired location for the additionof additives that catalyze the decomposition of hydrogen peroxide toeach scrubber may be downstream of each scrubber's recycle line orsidestream pump, as shown, for example, by the relative location of theadditive addition via the valve 130 to the pump 122 in FIG. 1. It shouldbe appreciated, however, that the desired location for the addition ofother additives may vary according to the particular additive used. Forexample, as described above, in using ozone as the catalyst, anair/ozone mixture may be added directly to a regenerative turbine pumpin the recycle line or sidestream of each scrubber. Alternatively, aregenerative turbine pump may be used to pump hydrogen peroxide from itssource container to a main header line that is fluidly connected to eachscrubber, wherein an air/ozone mixture is added to that regenerativeturbine pump rather than to each pump in each recycle line orsidestream.

Desired locations for the addition of acid or base for pH control inthis alternative embodiment include upstream of each scrubber's recycleor sidestream pump, such as shown by the relative location of theadditive addition via the valve 126 to the pump 122 in FIG. 1 and insome embodiments upstream of the addition point for the hydrogenperoxide also as shown in FIG. 1. In this alternative, the hydrogenperoxide may be added, for example, in the same manner as describedabove in connection with FIG. 1B.

Generally, it should be appreciated that the addition of the variouscomponents comprising the aqueous hydrogen peroxide composition may beadded at various locations throughout the scrubber system and are notlimited to those described in the above embodiments. For example, thehydrogen peroxide and other additives may be added at other locations inthe recycle line or sidestream or directly to the reservoir or tank,although some of these locations are more desirable than others, asdiscussed in the embodiments above.

FIG. 1C shows a diagram for a system for adding an oxidizer to one ormore gas/liquid contactors or scrubbers. A feed tank 180 is used to holdthe oxidizer, which may include hydrogen peroxide or another oxidizersuch as chlorine gas, sodium hypochlorite, hypobromous acid, chlorinedioxide, hydrogen peroxide, peroxy acids, ozone, and permanganate. Thefeed tank 180 may also have a level controller 182 that functions toprovide an alert when the tank level is low and additional hydrogenperoxide and/or water is required. It should be appreciated that certainadditives may also be added to the feed tank 180 provided they arechemically compatible with an oxidizer, such as hydrogen peroxide, sothat their chemical activity is not lost prior to being added to thescrubber. It should also be appreciated that the system of FIG. 1C canbe used in conjunction with the system of FIG. 1B and further inconjunction with a pH control loop.

The feed tank 180 is fluidly connected to a distribution pump 184 thatis fluidly connected to each scrubber's recycle line or sidestream (notshown) via a flow control valve 186 at the desired location along eachrecycle line or sidestream. One desired location for distributing theoxidizer from the feed tank 180 to each recycle line or sidestream maybe upstream of each scrubber's recycle line or sidestream pump, asshown, for example, by the relative location of the additive additionvia the valve 126 to the pump 122 in FIG. 1. It should be appreciated,however, that the point of addition to each scrubber may vary fromscrubber to scrubber and may include points other than the recycle lineor other or additional points along the recycle line. In other words,the oxidizer may be added to different locations along each scrubber'srecycle line or at different points for each scrubber, such as eachscrubber's reservoir.

In operation, the addition rate of the oxidizer from the feed tank 180to each recycle line or sidestream of each scrubber may be controlled invarious manners. In some embodiments, the addition of the oxidizer issimply set a given feed rate for each scrubber using the flow controlvalve 186. In other embodiments, different solution parameters could bemonitored and used to control the addition rate of the oxidizer from thefeed tank 180 by the flow control valve 186. As noted above, oxidationreduction potential, the concentration of the decomposition additive ora particular chemical species indicative of the concentration of theadditive, the concentration of gaseous species absorbed by the scrubber,or a combination of these could be monitored and used to control theaddition rate of the oxidizer from the feed tank 180. Of course, theconcentration of the oxidizer will need to be accounted for indetermining its addition rate to each scrubber or visa versa.

It should be appreciated that using a flow control valve 186 allows formore precise control of the flow rate to each scrubber, as opposed to asimple on/off valve. Particularly, by monitoring a given solutionparameter in the recycle stream, as shown in FIGS. 1 and 1A, thecomposition of the solution that is contacting the gas stream is betterknown than, for example, monitoring the solution in the reservoir.Further, by adding the oxidizer directly to the recycle stream basedupon the results of monitoring of the solution in the recycle streamallows the recycle stream chemistry to be properly controlled oradjusted just prior to entering the scrubber. This allows for moreoptimal control of the removal of the noxious and odorous components.However, it should be appreciated that in one embodiment it is desirableto simply set the addition rate of the oxidizer to a given, constantvalue and to adjust the addition rate of any additives (e.g., adecomposition additive in the case of using hydrogen peroxide as theoxidizer) accordingly.

Optionally, any make-up water required for each reservoir may also beadded to the feed tank 180 (not shown). In this case, the dilutioneffect of any water added to the feed tank 180 must be taken intoaccount so that the desired amount of each additives and acid or baseare ultimately added to each recycle line. In addition, the watermake-up needs of each reservoir, to the extent that they are different,must be taken into account. In other words, a water balance must beachieved for the overall system, which will also impact the amount ofwater in the feed tank 180, as discussed above. Alternatively, make-upwater may be added directly to each scrubber's reservoir.

As mentioned above, the liquid effluent produced by the presentinvention also offers advantages to influent to the wastewater treatmentprocess. For example, when using ferrous sulfate as the additive tocatalyze the decomposition of the hydrogen peroxide, the gas/waterscrubber water, e.g., the liquid effluent, can be evacuated to awastewater treatment facility, for example, by dumping the entire liquidcontent of the reservoir or by continuous overflow of from the reservoiror recycle line or sidestream, and this stream will have beeneffectively “pretreated” by cationic ferric hydroxide complexes thatoffer effective colloidal charge neutralization as well as the abilityto adsorb wastewater constituents into its floc matrix. The addition ofa charge neutralizing/adsorption species is always an added cost at thewastewater treatment plant. By use of the present invention that cost iseliminated or greatly reduced.

FIG. 2 shows the system of FIG. 1 within a wastewater effluent system ofa processing plant illustrating the pre-treatment properties of thepresent invention on the waste treatment facility according to oneembodiment of the present invention. In FIG. 2, liquid effluent isdischarged from the system 100 earlier described with reference to FIG.1, for example, through a wastewater pathway 202. As earlier described,the liquid effluent may be discharged by dumping the reservoir or bycontinual overflow of the liquid effluent from the reservoir. Thewastewater pathway 202 may merge with other wastewater pathways 204exiting from other process areas 206 in the processing plant, forexample, wash and rinse waters, chicken feather processing waters,rendering cooker waters, etc. These wastewater pathways 202, 204eventually converge into one or more wastewater pathways 208 thatdischarge into one or more large reservoirs in a wastewater treatmentfacility 210.

When the liquid effluent enters the reservoir at the wastewatertreatment facility 210, the liquid effluent is effectively“pre-treated”. The liquid effluent contains metal hydroxide complexes,for example, cationic ferric hydroxide complexes, that offer effectivecolloidal charge neutralization, as well as provide for adsorption ofwastewater constituents into its floc matrix. While some of thecomplexes are utilized by the components of the liquid effluent, aresidual amount of these complexes are also available to the otherwastewater effluent in the reservoir of the wastewater treatmentfacility. As wastewater treatment facilities typically purchaseadditives to accomplish these results, the addition of these chargeneutralizing and adsorption species eliminates or greatly reduces anycosts incurred by the waste treatment facility.

The present invention has been described above with reference to removalof odor and/or noxious components from an atmospheric effluent in whichthe oxidized odor and/or noxious components are oxidized during contactwith an aqueous hydrogen peroxide composition to produce a substantiallynon-odor offensive, environmentally acceptable by-product that issolubilized in or adsorbed onto the aqueous hydrogen peroxidecomposition to form a liquid effluent, and the advantages of such asystem provided to wastewater treatment processes. The present inventionalso has application in other areas of processing plants as an effectivebiocide, especially in areas related to aqueous food transport flumes.

Food primary and secondary processing involves the handling of largeamounts of organic materials. As a result of the amount of organicsbeing processed, biological activity is inevitable. In fruit andvegetable processing, large amounts of water are used to wash andtransport food through the various processing steps. Because of thebuildup of organic matter, the transport and wash waters are very proneto biological growth, as well as accumulation of toxic organic materialssuch as herbicides and pesticides. A need exists to provide microbialcontrol of these waters without imparting further toxic products to theaqueous food contact streams. Also needed is an economical method foreliminating or reducing the buildup of toxic herbicides and pesticidesin the food transport system.

Attempts in the art have been made utilizing oxidizing compounds such aschlorine gas, sodium hypochlorite, hypobromous acid, chlorine dioxide,hydrogen peroxide, peroxy acids, ozone, and permanganate. While some areeffective in limiting microbial growth, either toxic by-products, cost,or inefficiencies are limiting factors.

Particularly, the use of chlorine and chlorine dioxide, while effectiveantimicrobial agents, has come under environmental scrutiny due to thetoxic by-products it produces. When contacted with amines, toxicchloramines are formed, as well as trihalomethane compounds, which arenow prevalent in most ground waters in the United States. Chlorine-basedtechnologies also use large quantities of these materials, as they arerapidly consumed by the high organic loading of the aqueous media beforethey can impart antimicrobial properties. Hypobromous acid produced bythe decomposition of sodium bromide by chlorine has been used with somesuccess, but it too is affected by high organic loading and the chlorinesubstrates, which, while reduced, still impart the same toxicities ashypochlorous acid.

Hydrogen peroxide has been used with limited success. Hydrogen peroxideis a slow reacting compound with known antimicrobial properties. Thereaction rates are too slow for effective, cost advantageous microbialcontrol. Peroxy acids such as peracetic acid have proven to be effectiveantimicrobial compounds in aqueous systems. Peracids are usuallymanufactured by the combination of hydrogen peroxide, acetic acid, andinorganic acid catalyst, and various wetting and sequestering agents.Peracetic acid is normally provided in 5 to 15% peracetic acidconcentrations. These peracid compounds contain large amounts of themanufacturing precursors, such as hydrogen peroxide, and acetic acid.These peroxy acid materials have a strong pungent odor and residualacetic acids are toxic by ingestion or exposure at 10 ppm in mistedform. Peroxy acids are also limited in use by the high costs that areassociated with it. Ozone has found limited use in aqueous foodtransport and processing streams. Ozone is an effective biocide and itshigh electronegativity is capable of breaking down selected organiccompounds. Ozone is associated with extremely high capital investmentscost, and the efficiency is limited by poor transfer coefficients fromthe generated ozone gas phase to the liquid media being treated.

Use of the present invention, however, in which an aqueous hydrogenperoxide composition of hydrogen peroxide decomposed by ozone iscontacted with the transport waters, results in an effective biocide.This allows sterilization of food transport waters with no toxicby-products. Further, in food transport flumes, regulation of the ozonecan also break down accumulated pesticide and herbicide compounds fromfruit and vegetable washing into simple non-toxic carboxylic acids.Accordingly, this technology offers significant cost and efficiencyadvantages over current technologies.

EXAMPLES

The following examples describe specific aspects of the presentinvention to illustrate the invention and aid those of skill in the artin understanding and practicing the invention. The examples should notbe construed as limiting the present invention in any manner.

Example #1

A 1000 ml sample of chicken feather processing scrubber water having apH of 5.5 due to sulfuric acid addition in the scrubber reservoir wasevaluated. The sample had an intense odor after treatment with chlorinedioxide. The sample was treated concurrently with 300 ppm of hydrogenperoxide (50% solution) and 100 ppm ferrous sulfate (38% solution). Thereaction was instantaneous, and there was no detectable odor, other thana slight chlorine smell.

Example #2

A 1000 ml sample from a rendering cooker was adjusted to pH 5.5 withsulfuric acid. The sample had a very intense odor. The sample wastreated concurrently with 300 ppm of hydrogen peroxide (50% solution)and 100 ppm ferrous sulfate (38% solution). The reaction wasinstantaneous, and the odor was eliminated within 15 seconds. The samplewas then undisturbed for 48 hours, and there was no re-occurrence of anyodor.

Example #3

A five gallon sample from a rendering cooker was adjusted to pH 5.5. Thesample was recirculated at 10 gpm through a Burks regenerative turbinepump throttled by pinch valve assembly to 100 psi. Hydrogen peroxide wasintroduced into the suction line at 300 ppm. Ozone as a 6% gas streamgenerated by a corona discharge type ozonater on dried air was addedinto the air inlet for the Burks pump (suction side). The ozone dose was10 ppm as ozone. The sample was recirculated for 2 minutes, and odorswere completely neutralized. The sample was then un-aerated andundisturbed for 48 hours, and there was no re-occurrence of any odor.

Example #4

A trial was performed at a mixed proteins rendering plant that usedchlorine dioxide in a scrubber to reduce VOC emissions by 88%. In thissystem, the pH was reduced to pH 5.5 with sulfuric acid. 300 ppm ofhydrogen peroxide (50% solution) and 100 ppm ferrous sulfate (38%solution) were added concurrently. As a result, VOC emissions werereduced by 96%.

In the above examples, odor reduction was measured using the sense ofsmell and VOC emission measurements using standard emission detectors.It will be appreciated that various other devices and measurementtechniques may also be used that conform to standard practices as may berequired for a particular processing industry.

Example #5

A pilot plant test using hydrogen peroxide decomposed by ozone wasconducted to evaluate microbiological control. The test or run wasperformed using 100 gallons and a Pennsylvania apple wash/transportflume with the following characteristics: BOD=900 ppm, COD=2100 ppm, anda significant amount of large organic matter. The material wasrecirculated for 36 hours and the following data was collected: biocount via dip slide=109, filtered BOD (0.45 micron)=685 ppm, filteredCOD (0.45 micron)=1725 ppm.

300 ppm hydrogen peroxide (50% solution) was added, and ozone was addedat 10 ppm into a regenerative turbine pump used to recirculate solution.When the addition of hydrogen peroxide and ozone was completed theaddition was stopped. The following bio count in colonies was observed:@ t=4 min bio count=102, @ t=10 min bio count=none detected, @ t=8 hoursbio count=none detected, @ t=12 hours bio count=10, and @ t=18 hours biocount=102. Additional data included: filtered BOD=210 ppm and filteredCOD=720 ppm.

As can be seen by this test, microbial control was excellent with goodsustained kill of biopopulation. The lowering of the COD showeddecomposition of organic material in the sample water. Analysis fortoxicity indicated a sharp drop.

Although the foregoing invention has been described in some detail tofacilitate understanding, it will be apparent that certain changes andmodifications may be practiced within the scope of the appended claims.Accordingly, the described embodiment is to be considered asillustrative and not restrictive, and the invention is not to be limitedto the details given herein, but may be modified within the scope andequivalents of the appended claims.

1. A method for removing an odorous or noxious component from a gasstream, comprising: adding hydrogen peroxide, a hydrogen peroxidedecomposition additive, and a chelating agent to a liquid stream;contacting a gas stream comprising at least one odorous or noxiouscomponent with said liquid stream; and absorbing at least a portion ofsaid odorous or noxious component in said gas stream into said liquidstream.
 2. The method of claim 1, wherein said hydrogen peroxidedecomposition additive comprises ferric sulfate.
 3. The method of claim2, wherein said chelating agent is selected from the group consisting ofaminopolycarboxylates, polyhydroxy aromatics, and combinations thereof.4. The method of claim 3, wherein said chelating agent is selected fromthe group consisting of nitrilotriacetic acid, hydroxyethyliminodiaceticacid, and combinations thereof.
 5. The method of claim 2, wherein saidchelating agent comprises picolinic acid.
 6. The method of claim 2,wherein said chelating agent comprises gallic acid.
 7. The method ofclaim 2, wherein said chelating agent comprises rhodizonic acid.
 8. Themethod of claim 2, wherein said chelating agent comprisestetrahydroxy-1,4-quinone.
 9. The method of claim 2, wherein saidchelating agent comprises hexaketocyclohexane.
 10. The method of claim2, wherein said chelating agent is selected from the group consisting ofpicolinic acid, gallic acid, rhodizonic acid, tetrahydroxy-1,4-quinone,hexaketocyclohexane, and combinations thereof.
 11. The method of claim1, wherein said hydrogen peroxide decomposition additive comprisesferrous sulfate.
 12. The method of claim 1, further comprising measuringa measurable parameter of said liquid stream, wherein said addingcomprises separately adding said hydrogen peroxide and said hydrogenperoxide decomposition additive to said liquid stream and wherein saidadding said decomposition additive comprises adding said decompositionadditive at a rate based upon said measuring.
 13. The method of claim 1,further comprising controlling a pH of said liquid stream by adding acidor base to said liquid stream.
 14. The method of claim 1, wherein saidadding comprises separately adding said hydrogen peroxide and saidhydrogen peroxide decomposition additive to said liquid stream.
 15. Themethod of claim 14, further comprising controlling a pH of said liquidstream.
 16. The method of claim 15, further comprising mixing acid orbase with said hydrogen peroxide decomposition additive prior to saidseparately adding, wherein said separately adding comprises adding saidacid or said base and said hydrogen peroxide decomposition additive at arate and wherein said controlling of said pH comprises controlling saidrate of said separately adding.
 17. The method of claim 1, wherein saidcontacting comprises counter-currently contacting said gas stream andsaid liquid stream and further comprising: recycling said liquid streamafter said counter-current contacting to produce a recycle liquidstream; repeating said counter-currently contacting wherein said liquidstream comprises said recycle liquid stream; and controlling a pH ofsaid recycled liquid stream at a value higher than a pH of said recycleliquid stream without said chelating agent; wherein said addingcomprises adding said hydrogen peroxide, said hydrogen peroxidedecomposition additive, and said chelating agent to said recycle liquidstream.
 18. The method of claim 17, wherein said hydrogen peroxidedecomposition additive comprises ferric sulfate.
 19. The method of claim18, wherein said chelating agent is selected from the group consistingof aminopolycarboxylates, polyhydroxy aromatics, and combinationsthereof.
 20. The method of claim 19, wherein said chelating agent isselected from the group consisting of nitrilotriacetic acid,hydroxyethyliminodiacetic acid, and combinations thereof.
 21. The methodof claim 18, wherein said chelating agent is selected from the groupconsisting of picolinic acid, gallic acid, rhodizonic acid,tetrahydroxy-1,4-quinone, hexaketocyclohexane, and combinations thereof.22. The method of claim 17, wherein said hydrogen peroxide decompositionadditive comprises ferrous sulfate.
 23. The method of claim 17, whereinsaid adding comprises separately adding said hydrogen peroxide and saidhydrogen peroxide decomposition additive to said recycle liquid stream.24. The method of claim 23, further comprising mixing acid or base withsaid hydrogen peroxide decomposition additive prior to said separatelyadding, wherein said separately adding comprises adding said acid orsaid base and said hydrogen peroxide decomposition additive at a rateand wherein said controlling of said pH further comprises controllingsaid rate of said separately adding.
 25. A method for removing anodorous or noxious component from a gas stream, comprising: addinghydrogen peroxide and ozone to a liquid stream; contacting a gas streamcomprising at least one odorous or noxious component with said liquidstream, wherein said contacting comprises counter-currently contactingsaid gas stream and said liquid stream, recycling said liquid streamafter said counter-current contacting to produce a recycle liquidstream, and repeating said counter-currently contacting wherein saidliquid stream comprises said recycle liquid stream; and absorbing atleast a portion of said odorous or noxious component in said gas streaminto said liquid stream; wherein said adding comprises adding saidhydrogen peroxide and said ozone to said recycle liquid stream andfurther comprising controlling a pH of said recycle liquid stream byadding acid or base to said recycle liquid stream.
 26. The method ofclaim 25, wherein said adding comprises adding hydrogen peroxide andozone to said recycle liquid stream concurrently.
 27. The method ofclaim 25, wherein said adding comprises separately adding said hydrogenperoxide and said ozone to said recycle liquid stream.
 28. The method ofclaim 27, further comprising controlling a pH of said recycle liquidstream by adding acid or base to said recycle liquid stream.
 29. Amethod for removing an odorous or noxious component from a gas stream,comprising: adding an oxidizer to a liquid stream; adding an additive tosaid liquid stream; contacting a gas stream comprising at least oneodorous or noxious component with said liquid stream; absorbing at leasta portion of said odorous or noxious component in said gas stream intosaid liquid stream; measuring a measurable parameter of said liquidstream to produce a value for said measurable parameter; and controllingautomatically said adding of said additive to said liquid stream basedupon said value.
 30. The method of claim 29, wherein said oxidizercomprises hydrogen peroxide and said additive comprises a hydrogenperoxide decomposition additive.
 31. The method of claim 30, whereinsaid adding of said hydrogen peroxide and said adding of said hydrogenperoxide decomposition additive are performed separately.
 32. The methodof claim 31, wherein said controlling automatically of said adding ofsaid hydrogen peroxide decomposition additive is performed using ananalog flow control valve.
 33. The method of claim 31, furthercomprising mixing acid or base and said hydrogen peroxide decompositionadditive prior to said adding of said hydrogen peroxide decompositionadditive to said liquid stream and wherein said measurable parametercomprises pH.
 34. The method of claim 33, wherein said controllingautomatically of said adding of said hydrogen peroxide decompositionadditive is performed using an analog flow control valve.
 35. The methodof claim 29, wherein said measurable parameter is a concentration ofsaid additive in said liquid stream.
 36. The method of claim 35, furthercomprising: mixing acid or base and said additive prior to said addingof said additive to said liquid stream; controlling a pH of said liquidstream; and wherein said controlling automatically of said adding ofsaid additive and said controlling of said pH are each separatelyperformed using separate analog flow control valves.
 37. The method ofclaim 29, wherein said measurable parameter is an oxidation reductionpotential of said liquid stream and wherein said adding of said additiveto said liquid stream comprises adding said additive to said liquidstream at a rate based upon said oxidation reduction potential of saidliquid stream.
 38. The method of claim 37, further comprising: mixingacid or base and said additive prior to said adding of said additive tosaid liquid stream; controlling a pH of said liquid stream; and whereinsaid controlling automatically of said adding of said additive and saidcontrolling of said pH are each separately performed using separateanalog flow control valves.
 39. The method of claim 37, wherein saidoxidizer comprises hydrogen peroxide and said additive comprises ahydrogen peroxide decomposition additive.
 40. The method of claim 39,wherein said adding of said hydrogen peroxide and said adding of saidhydrogen peroxide decomposition additive are performed separately. 41.The method of claim 40, wherein said controlling automatically of saidadding of said hydrogen peroxide decomposition additive is performedusing an analog flow control valve.
 42. The method of claim 41, furthercomprising mixing acid or base and said additive prior to said adding ofsaid additive to said liquid stream; controlling a pH of said liquidstream; and wherein said controlling automatically of said adding ofsaid additive and said controlling of said pH are each separatelyperformed using separate analog flow control valves.